Resin composition, molding material, and molded object

ABSTRACT

A phenolic resin composition in which the phenolic resin can be smoothly cured at a low temperature while inhibiting the generation of free formaldehyde and trapping free phenol. An epoxy compound is dispersed or dissolved as a hardener in an aqueous phenolic resin solution. The epoxy compound functions not only as a hardener for the phenolic resin but as a trapping agent for free phenol. The phenolic resin has been sulfoalkylated and/or sulfialkylated so as to have improved hydrophilicity.

FIELD OF THE INVENTION

[0001] The present invention relates to a resin composition used as animpregnating material, binder, paint, adhesive and the like, a moldingmaterial using said resin composition, and a molded article using saidmolding material.

BACKGROUND OF THE INVENTION

[0002] Up to now phenolic resin has been used as an impregnatingmaterial for fiber sheets and the like, a binder of wood flake, fibermaterial and the like, paint, adhesive and the like, and formaldehyde orformaldehyde donor such as hexamethylenetetramine and the like are usedas a curing agent of said phenolic resin.

[0003] Nevertheless in a case where said curing agent is used, saidcuring agent emits formaldehyde when phenolic resin is cured, andfurther formaldehyde remains in phenolic resin after curing so thatthere is problem that formaldehyde emitted from the molded articlemanufactured by molding and curing the molding material in whichphenolic resin is impregnated contaminates environment. Accordingly, theobject of the present invention is to provide a resin composition and amolding material impregnated with said resin composition and a moldingarticle of designated shape which is molded out of said molding materialwhich emit no formaldehyde which emits no formaldehyde when or aftersaid resin composition is cured.

DISCLOSURE OF THE INVENTION

[0004] To solve above described problem, the present invention providesa molding material comprising of a porous material impregnated with saidresin composition comprising aqueous solution of phenolic resin andepoxy compound. In said resin composition with which said moldingmaterial is impregnated, since said epoxy compound acts as a curingagent of phenolic resin, it is not necessary to use formaldehyde orformaldehyde donor such as hexamethylenetetramine as curing agent sothat said resin composition does not emit formaldehyde, when or aftersaid resin composition is cured, not to contaminate environment.

[0005] In said resin composition with which said molding material isimpregnated, aminoplast monomer and/or its precondensate may beco-condensated with said phenolic resin and further, aminoplast resinand/or aminoplast monomer may be mixed in said resin composition.

[0006] Furthermore, in said resin composition with which said moldingmaterial is impregnated, said epoxy compound is desirably dispersed oremulsified in water and then mixed in said aqueous solution of phenolicresin and it is desirable that said phenolic resin is partially orwholly sulfoalkylated and/or sulfialkylated.

[0007] Still further, said epoxy compound is desirably epoxy resin andin this case said epoxy resin has desirably aryl group and moredesirably said aryl group is partially or wholly sulfoalkylated and/orsulfialkylated.

[0008] In said molding material, said phenolic resin in said resincomposition is desirably to be in B-stage.

[0009] In addition, the present invention provides a molding articlemanufactured by molding said molding material with heating in adesignated shape to cure said resin composition in said moldingmaterial.

[0010] Additionally, the present invention provides a molding materialconsisting of chip and/or powder and/or fiber material in which a resincomposition comprising of a mixture of aqueous solution of phenolicresin and epoxy compound is mixed as a binder and a molded articlemanufactured through molding said molding material by heating into adesignated shape, curing said resin composition in said moldingmaterial.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIGS. 1 to 3 show an embodiment of the present invention.

[0012]FIG. 1 is to illustrate a process to manufacture a molded article.

[0013]FIG. 2 is to illustrate a process to manufacture a molded article.

[0014]FIG. 3 is to illustrate a process to manufacture a molded article.

[0015] In the drawings,

[0016] (11) base member

[0017] (12) cured sheet

PREFERRED EMBODIMENT

[0018] A. Resin Composition

[0019] Necessary components of said resin composition of the presentinvention are aqueous solution of phenolic resin and epoxy compoundwhich is dispersed or dissolved in said phenolic resin.

[0020] [Phenolic resin]

[0021] Phenolic resin is produced by condensation reaction betweenphenolic compound and aldehyde and/or aldehyde donor. In the case ofwater soluble phenolic resin, sulfoalkylated and/or sulfialkylatedphenolic resin is desirably used to improve stability. Not only saidphonolic resin but, for instance, novolak resin produced by condensationreaction between cresol including m-cresol and p-cresol and carbonylcompound and the like (TOKKAI Hei 11-322874) is also used as watersoluble phenolic resin besides said phenolic resin in the presentinvention.

[0022] (Phenolic compound)

[0023] Phenolic compound used to produce said phenolic resin may bemonohydric phenol or polyhydric phenol or a mixture of monohydric phenoland polyhydric phenol, but in a case where only monohydric phenol isused, formaldehyde is apt to be emitted when or after said resincomposition is cured so that polyphenol or a mixture of monophenol andpolyphenol is desirably used.

[0024] (Monohydric Phenol)

[0025] The monohydric phenols include alkyl phenols such as o-cresol,m-cresol, p-cresol, ethylphenol, isopropylphenol, xylenol, 3,5-xylenol,butylphenol, t-butylphenol, nonylphenol and the like; monohydricderivatives such as o-fluorophenol, m-fluorophenol, p-fluorophenol,o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol,m-bromophenol, p-bromophenol, o-iodophenol, m-iodophenol, p-iodophenol,o-aminophenol, m-aminophenol, p-aminophenol, o-nitrophenol,m-nitrophenol, p-nitorophenol, 2,4-dinitorophenol, 2,4,6-trinitorophenoland the like; monohydric phenols of polycyclic aromatic compounds suchas naphthol and the like. Each monohydric phenol can be used singly orused as a mixture thereof.

[0026] (Polyhydric Phenol)

[0027] The polyhydric phenols mentioned above, include resorsin,alkylresorsin, pyrogallol, catechol, alkyl catechol, hydroquinone, alkylhydroquinone, fluoroglrsin, bisphenol, dihydroxynaphthalene and thelike. Each polyhydric phenol can be used singly of used as a mixturethereof. Resorsin and alkylresorsin are more suitable than otherpolyhydric phenols. The alkylresorsin is the most suitable polyhydricphenols in particular because the alkylresorsin can react with aldehydesrapidly than the resorsin. The alkylresorsins include 5-methyl resorsin,5-ethyl resorsin, 5-propyl resorsin, 5-n-butyl resorsin, 4,5-dimethylresorsin, 2,5-dimethyl resorsin, 4,5-diethyl resorsin, 2,5-diethylresorsin, 4,5-dipropyl resorsin, 2,5-dipropyl resorsin, 4-methyl-5-ethylresorsin, 2-methyl-5-ethyl resorsin, 2-methyl-5-propyl resorsin,2,4,5-trimethyl resorsin, 2,4,5-triethyl resorsin, and the like.

[0028] Polyhydric phenol mixture produced by dry distillation of oilshale produced in Estonia is inexpensive and said polyhydric phenolmixture includes 5-metylresorcin and many kinds of alkylresorcin havinga high reactivity so that said polyhydric phenol mixture is a speciallydesirable polyphenol raw material.

[0029] In the present invention, said phenolic compound and aldehydeand/or aldehyde donor (aldehydes) are condensated together. Saidaldehyde donor means a compound or a mixture which emits aldehyde whensaid compound or said mixture decomposes. The aldehydes includeformaldehyde, acetoaldehyde, propionaldehyde, chloral, furfural,glyoxal, n-butylaldehyde, caproaldehyde, allylaldehyde, benzaldehyde,crotonaldehyde, acrolein, phenyl acetoaldehyde, o-tolualdehyde,salicylaldehyde and the like. The aldehyde donors includeparaformaldehyde, tiroxane, hexamethylenetetramine, tetraoxymethyleneand the like.

[0030] As above described, said phenolic resin is desirablysulfoalkylated and/or sulfialkylated to improve the stability of saidwater soluble phenolic resin.

[0031] (Sulfoalkylation Agent)

[0032] The sulfoalkylation agents for use to improve stability ofaqueous solution of phenol resins, include water soluble sulfitesprepared by reaction of sulfurous acid, bisulfurous acid, ormetabisulfirous acid and alkaline metals, trimethyl amine, quaternaryammonium (e.g. benzyltrimethylammonium); aldehyde additions prepared byreaction of water soluble sulfites and aldehydes.

[0033] The aldehyde additions are prepared by addition reaction ofaldehydes and water soluble sulfites mentioned above, wherein thealdehydes include formaldehyde, acetoaldehyde, propionaldehyde, chloral,furfural, glyoxal, n-butylaldehyde, caproaldehyde, allylaldehyde,benzaldehyde, crotonaldehyde, acrolein, phenyl acetoaldehyde,o-tolualdehyde, salicylaldehyde and the like. For example,hydroxymethane sulfonate, which is one of the aldehyde additions, isprepared by addition reaction of formaldehyde and sulfite.

[0034] (Sulfialkylation Agent)

[0035] The sulfialkylation agents for use to improve stability ofaqueous solution of phenol resins, include alkaline metal sulfoxylatesof aliphatic or aromatic aldehyde such as sodium formaldehydesulfoxylate (a.k.a. Rongalit), sodium benzaldehyde sulfoxylate and thelike; hydrosulfites (a.k.a. dithionites) of alkaline metal or alkalineearth metal such as sodium hydrosulfite, magnesium hydrosulfite and thelike; hydroxyalkanesulfinate such as hydroxymethanesulfinate and thelike.

[0036] (Additive)

[0037] In the case of producing the phenol resins, if necessary,additives may be mixed with the phenol resins as a catalyst or to adjustpH, wherein additives include acidic compounds and alkaline compounds.Acidic compounds include inorganic acid or organic acid such ashydrochloric acid, sulfuric acid, orthophosphoric acid, boric acid,oxalic acid, formic acid, acetic acid, butyric acid, benzenesulfonicacid, phenolsulfonic acid, p-toluenesulfonic acid,naphthalene-α-sulfonic acid, naphthalene-β-sulfonic acid and the like;esters of organic acid such as dimethyl oxalate and the like; acidanhydrides such as phthalic anhydride, maleic anhydride and the like;salts of ammonium such as ammonium chloride, ammonium sulfate, ammoniumnitrate, ammonium oxalate, ammonium acetate, ammonium phosphate,ammonium thiocyanate, ammonium imidosulfonate and the like; halogenatedorganic compounds such as monochloroacetic acid, salt thereof,α,α′-dichlorohydrin and the like; hydrochloride of amines such astriethanolamine hydrochloride, aniline hydrochloride and the like; ureaadducts such as urea adduct of salicylic acid, urea adduct of stearicacid, urea adduct of heptanoic acid and the like; N-trimethyl taurine,zinc chloride, ferric chloride and the like.

[0038] Alkaline compounds include ammonia, amines; hydroxides ofalkaline metal and alkaline earth metal such as sodium hydroxide,potassium hydroxide, barium hydroxide, calcium hydroxide and the like;oxide of alkaline earth metal such as lime and the like; salts ofalkaline metal such as sodium carbonate, sodium sulfite, sodium acetate,sodium phosphate and the like.

[0039] (Method of Producing the Phenol Resins)

[0040] The phenol resins (the precondensation polymers) can be preparedby usual method. The usual method includes method (a) comprisingcondensation of a monohydric phenol and/or a polyhydric phenol and thealdehydes; method (b) comprising condensation of a precondensationpolymer and a monohydric phenol and/or a polyhyrdric phenol, wherein theprecondensation polymer comprises a monohydric phenol and aldehydes;method (c) comprising condensation of a precondensation polymer and amonohydric phenol and/or a polyhydric phenol, wherein theprecondensation polymer comprises a monohydric phenol, a polyhydricphenol and aldehydes; method (d) comprising condensation of aprecondensation polymer consisting of the monohydric phenol and thealdehydes, and the precondensation polymer consisting of the polyhydricphenol and the aldehydes; method (e) comprising condensation of theprecondensation polymer consisting of the monohydric phenol and thealdehydes and/or the precondensation polymers consisting of thepolyhydric phenol resin and the aldehydes, and the precondensationpolymer consisting of the monohydric phenol and the polyhydric phenoland the aldehydes.

[0041] In the case of the method (a) of the condensation of themonohydric phenol and/or the polyhydric phenol and the aldehydes, thealdehydes (0.2 mole to 3 moles) are added to the monohydric phenol (1mole), and the aldehydes (0.1 mole to 0.8 mole) are added to thepolyhydric phenol (1 mole) in usual. If necessary, additives may beadded to the phenol resins (the precondensation polymers). In themethod(a), the condensation is reacted by heating at 55° C. to 100° C.for 8 hrs to 20 hrs. Addition of the aldehydes may be done at one timeat the beginning of the reaction, or several times during the reaction.The acid compounds or alkaline compounds mentioned above are used as acatalyst of the condensation reaction. The novolak type phenol resinsare the suitable resins in this invention so that the acid compounds areused as the catalyst. The novolak type phenol resins have littleformaldehyde and good reactivity with the epoxy compounds.

[0042] In the case of sulfomethylation and/or sulfimethylation, thesulfomethylation agents and/or sulfimethylation agents may be added tothe precondensation on a suitable occasion.

[0043] Addition of the sulfomethylation agents and/or sulfimethylationagents may be done any time such as before the beginning of thecondensation, during the condensation or after the condensation.

[0044] Total addition amount of said sulfoalkylation agent and/orsulfialkylation agent is usually in the range between 0.001 to 1.5 molesfor 1 mole of phenol. In a case where said addition amount is less than0.001 mole, hydrophile of the resulting sulfoalkylated and/orsulfialkylated phenolic resin is not enough and in a case where saidaddition amount is more than 1.5 moles, water resistance of theresulting sulfoalkylated and/or sulfialkylated phenolic resin becomesinferior. To provide excellent using property of the resultingprecondensate and excellent physical properties of the cured resin, saidaddition amount is preferably in the range between 0.01 to 0.8 mole for1 mole of phenol.

[0045] The sulfomethylation agents and/or sulfimathylation agents forsulfomathylation and/or sulfimethylation react with the methylol groupsand/or aromatic groups so that the sulfomethyl group and/or sulfimethylgroup are introduced to the precondensation prepolymers.

[0046] The solution of precondensation polymers of sulfoalkylated and/orsulfialkylated phenol resins is stable widely even if acid condition(e.g. pH=1.0) or alkaline condition so that the solution can be cured inany conditions such as acid, neutral or alkaline condition. In the caseof curing the precondensation under the acid condition, there is adecrease of remained methylol groups so that no formaldehydes fromdecomposed cured phenol resins occur.

[0047] Even if in the case of use of an insoluble epoxy compounds, thisinvention has an advantage of getting a stable epoxy compoundsdispersion to mix the epoxy compounds with a solution of precondensationpolymers of sulufomethylated and/or sulufimethylated phenol resins.Therefore the insoluble epoxy compounds can be dispersed in the solutioneasily.

[0048] Further, if necessary, the phenol resins and/or precpndensationpolymers thereof may be copolycondensated by amino resin monomers suchas urea, thiourea, melamine, thiomelamine, dicyandiamine, guanidine,guanamine, acetoguanamine, benzoguanamine, 2,6-diamino-1.3-diamine andthe like.

[0049] [Epoxy Compound]

[0050] Epoxy compounds for use in this invention have at least two epoxygroups. The epoxy compounds include poly epoxy compounds such asdiethylene glycol diglycidyl ether, polyethylene glycol diglycidylether, tripropylene glycol diglycidyl ether, polypropylene glycoldiglycidyl ether, glycerine polyglycidyl ether, polyglycerinepolyglycidyl ether, neopentyl grycol diglycidyl ether, 1,6-hexanedioldiglycidyl ether, trimethylol propane polyglycidyl ether, glycidylhexahydrophthalate, epoxy compounds modified fatty acid and the like;epoxy resins such as epoxy resins of bisphenol A, epoxy resins oftetrabromobisphenol A, epoxy resins of bisphenol F. epoxy resins ofbisphenol S, epoxy resins of bisphenol B, epoxy resins of naphthalene,epoxy resins of novolak resin, epoxy resins having fluorene structures,epoxy resins comprising copolymer of phenol compounds anddicyclopentadiene, epoxy resins of diglycidyl resorcinol, epoxy resinsof glycidyl ether, epoxy resins of glycidyl amine and the like; epoxyderivatives prepared by reacting epichlorohydrin and the polyhydricphenol mentioned above or bisphenol(e.g. bisphenol A, bisphenol F) andthe like. The epoxy compounds epoxy resins, epoxy derivatives can usesingly, or in combination with each other.

[0051] Epoxy derivatives have good reactivity with phenol resins so thatepoxy resins are the most suitable for use in this invention. Among ofall epoxy derivatives, the epoxy derivatives of polyhydric phenols (e.g.resorsin, alkyl resorsin, shale oil resorsin) can react with the phenolresins well in particular.

[0052] Said epoxy compound is desirably soluble or dispersible in waterconsidering easiness of dissolving or dispersing in aqueous solution ofphenolic resin or considering uniformity of mixture of said epoxycompound and said aqueous solution of phenolic resin and said epoxycompound is desirably dispersed or emulsified in water by using suitableemulsifier and then mixed in said aqueous solution of phenolic resin.However even water-insoluble epoxy compound can be dispersed andemulsified in said aqueous solution of phenol resin in which emulsifieris dissolved as it is or by dissolving in organic solvent. In a casewhere said phenolic resin is sulfoalkylated and/or sulfialkylated, evensaid epoxy compound is water-insoluble, said epoxy compound can bedispersed and emulsified in said aqueous solution of phenolic resinwithout using emulsifier since said sulfoalkylated and/or sulfialkylatedphenolic resin acts as a dispersing agent. Further, when epoxy resin isused as said epoxy compound, said resin composition of the presentinvention gives a cured resin having a high strength. In this case whensaid epoxy resin have aromatic hydrocarbon radical, said aromatichydrocarbon radical may be partially or wholly sulfoalkylated and/orsulfialkylated in the same manner as said phenolic resin, improvinghydrophilicity. In this case, sulfoalkylating agent and/orsulfialkylating agent is(are) added to epoxy resin monomer such asbisphenol in an amount of 0.001 to 1.5 mol, desirably 0.01 to 0.8 molfor epoxy resin monomer. In a case where said sulfoalkylating agentand/or sulfialkylating agent is added in an amount less than 0.001 molfor epoxy resin monomer, hydrophile of said epoxy resin may not beenough but in a case where said sulfoalkylating agent and/orsulfialkylating agent is added in an amount of bigger than 1.5, waterresistance may decrease.

[0053] One or more kind(s) of mono epoxy compound may be added to saidepoxy compound to improve flexibility or as reactive diluting agent.Said mono epoxy compound is such as higher alcohol glycidyl ether, butylglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether,nonylphenyl glycidyl ether, glycidyl methacrylate and the like.

[0054] [Resin Composition]

[0055] Said resin composition of the present invention contains saidwater-soluble phenolic resin and said epoxy compound and in said resincompound, said epoxy compound acts as a curing agent of said phenolicresin. Accordingly, it is not necessary to use formaldehyde orformaldehyde donor such as hexamethylenetetramine as curing agent ofsaid phenolic resin so that said resin composition contains littleamount of free formaldehyde when or after said resin composition iscured, as the result, said resin composition has no problem about thecontamination of environment. Further since said epoxy compound reactswith free phenol contained in said resin composition, as the result saidresin composition contains little amount of free phenol to preventgeneration of a bad smell from free phonol.

[0056] Adding amount of said epoxy compound to said phenolic resin isdesirably 2 to 150 parts by weight, more desirably 5 to 100 parts byweight for 100 parts by weight of said phenolic resin. When addingamount of said epoxy compound is less than 2 parts by weight, curing ofsaid phenolic resin is not enough and when adding amount of said epoxycompound is more than 150 parts by weight, the amount of epoxy compoundwhich is not combined with said phenolic resin increases to have badinfluence upon strength.

[0057] Usually said resin composition is provided as an aqueous solutionof precondensate. If necessary, epoxy resin curing agents includingamines such as aliphatic amines (e.g. ethylenediamine, diethylenetriamine, triethylene tetramine, dipropylene triamine,dimethylaminopropylamine, diethylaminopropylamine,cyclohexylaminopropylamine, monoethanolamine, diethanolamine,propanolamine, N-methylethanolamine, aminoethyletanolamine and thelike); aromatic amines (methanephenylenediamine,P,P′-diaminodiphenylmethane, diaminodiphenylsulfone,benzyldimethylamine, a-methyldimethylamine,dimethylaminomethylphenol, tridimethylaminomethylbenzene, and the like);acid anhydrides (e.g. phthalic anhydride, hexahydrophthalic anhydride,dodecylsuccinic anhydride, pyromellitic dianhydride, croleinticanhydride and the like) may be added to the phenol resins or epoxycompounds.

[0058] Further aldehydes such as formaldehyde, acetoaldehyde,propionaldehyde, chloral, furfural, glyoxal, n-butylaldehyde,caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein,phenyl acetoaldehyde, o-tolualdehyde, salicylaldehyde and the like;aldehyde donors such as paraformaldehyde, tiroxane,hexamethylenetetramine, tetraoxymethylene and the like; amino resinssuch as urea resins, melamine resins and the like; natural rubbers,derivatives thereof; synthetic rubbers such as styrene/butadiene rubber,acrylonitrile/butadiene rubber, chloroprene rubber, ethylene/propylenerubber, isoprene rubber, isoprene/isobutylene rubber and the like; vinylhompolymers or vinyl copolymers such as vinyl acetate, vinyl propionate,styrene, acrylate, metacrylate, acrylonitrile, acrylic acid, methacrylicacid, maleic acid, vinyl chloride, vinylidene chloride, vinylpyridineand the like; emulsions, latices, aqueous or solutions of polyurethane,polyamide, butyral resin, polyethylene, polypropylene, vinylacetate/ethylene copolymer, chlorinated polyethylene, chlorinatedpolypropylene, polyester and the like; water soluble polymers or naturalgums such as polyvinyl alcohol, sodium alginate, starch, starchderivatives, glue, gelatin, blood powder, methylcellulose,carboxymethylcellulose, hydroxymethylcellulose, polyacrylic acid,polyacrylic amide and the like; fillers such as calcium carbonate, talc,gypsum, carbon black, wood powder, walnut powder, coconut powder, wheatflour, rice flour and the like; surface active agent; higher fatty acidssuch as stearic acid, palmitin acid and the like; higher alcohols suchas palmityl alcohol, stearyl alcohol and the like; ester of fatty acidsuch as butylstearate, glycerin monosteatate and the like; amides offatty acid; natural wax such as carnauba wax and the like; syntheticwax; release agents such as paraffin, paraffin oil, silicone oil,silicone resin, fluororesin, polyvinylalcohol, grease and the like; lowboiling point solvents such as hexane, butane, n-pentane, alcohol,ether, methylene chloride, tetrachloromethane, chlorofluoromethane,1,1,2-trichloro-1,2,2-trifluoroethane and the like; organic foamingagents such as azodicarbonamide, dinitorosopentamethylenetetramine,P,P′-oxybis(benzensulfonyl hydrazide, azobis-2,2′-(2-methyl glopionitorile) and the like; inorganic foaming agents such as sodiumbicarbonate, potassium bicarbonate, ammonium bicarbonate and the like;microcapsule foaming agents consisting of a thermoplastic resin capsulein which include a gas such as n-pentane, isopentane, butane, isobuteneand the like; porous particles such as silas balloon, paerlite, glassballoon, foamed glass, porous ceramics and the like, plastic foam andpowder thereof such as polyethylene foam, polystyrene foam,polypropylene foam, pigment, dye, fire retardant, water repellent, oilrepellent, insect repellent(insecticide), antiseptic, antioxidant,ultraviolet absorber; plasticizers such as phthalate(e.g. dibutylphthalate(DBP), dioctyl phthalate (DOP), dicyclohexylphthalate),tricresyl phosphate and the like may be added to the phenol resinsand/or epoxy compounds.

[0059] In curing reaction of said resin composition of the presentinvention, phonolic hydroxy group of said phenlic resin reacts withepoxy groups besides said reaction, the reaction between aromatichydrocarbon radical of said phenolic resin and aromatic hydrocarbonradical of said epoxy compound to produce methylene bond also takesplace in a case where said resin composition contains formaldehyde orphenol component in said phenolic resin has methylol group.

[0060] Said resin composition above mentioned has various use such as animpregnating agent for porous material such as fiber sheets, foamedplastic sheets and the like to give said porous material rigidity andmoldability, a binder for wood flake, fiber material and the like,paint, adhesive, and the like.

[0061] B. MOLDING MATERIAL

[0062] Said resin composition of the present invention is impregnated inporous material as an impregnating agent or mixed in chip, powder, orfiber as a binder. Said porous material (molding material (1))impregnating said resin composition of the present invention, and saidchip, powder or fiber in which said resin composition is mixed (moldingmaterial (2)) have moldability so that they are useful as moldingmaterial.

[0063] [Porous Material]

[0064] Porous materials for use in this invention include fiber members,plastic foam and sintered plastic beads.

[0065] The fiber members include natural fiber such as cotton, hemp,wool, silk, kenaf, coconut fiber, bamboo fiber and the like; organicsynthetic fibers such as polyamide fiber, polyester fiber, acrylicfiber, viscose fiber, acetate fiber, vinyl chloride, vinylidene chlorideand the like, inorganic fibers such as asbestos fiber, glass fiber,carbon fiber, ceramics fiber, metal fiber, whisker, rock wool and thelike; recycled fibers prepared by untying waste articles made of thefiber members, mixed fiber thereof. Fiber member may be mixed withthermoplastic fiber having a melting point under 200° C. such aspolyester fiber, polypropylene fiber, polyethylene fiber, polyamidefiber and the like. The fiber members have a variety of style such asweb, nonwoven fabric, felt, knitted items, textile, laminates thereof,and the like.

[0066] Plastic foams, which are interconnecting foam, includepolyurethane; polyolefin foam such as polyethylene, polypropylene;polyvinyl chloride foam, polystyrene foam; amino resin foams such asmelamine foam, urea foam; phenol resin foam, and the like. Plastic foamsare prepared as plastic green sheets for use in automobiles' interiormember.

[0067] [Manufacturing of Molding Material (1)]

[0068] The molding material (1) of the present invention can bemanufactured by impregnating said resin composition of the presentinvention in said porous material and drying by heating at a temperaturelower than curing temperature of said resin composition.

[0069] Many well-known methods such as a dipping method, spray method,and the like can be applied to impregnate said resin composition in saidporous material. In the case of said dipping method, for instance, saidporous material is dipped in a dipping tank in which said resincomposition is filled and then said porous material to which said resincomposition adheres is pressed by a wringing roller or press plate orthe like to impregnate a desirable amount of said resin composition insaid porous material. Further said resin composition may be mechanicallyor chemically foamed.

[0070] Said porous material in which said resin composition isimpregnated is then dried by heating and in said heating and dryingprocess, said phenolic resin precondensate contained in said resincomposition may be put in B-stage. To keep said precondensate inB-stage, heating temperature, time and so on are conveniently adjustedand heating temperature is settled below curing temperature of saidresin composition, usually in the range between 50 and 180° C., andheating time is settled in the range between 0.1 and 5 hours. Usuallyhot air heating, far infrared radiation heating, high frequency heatingare applied for said heating and drying process.

[0071] As above described, phenol resin precondensate in said resincomposition impregnated in said porous material is put in B-stage and inthis case, the stability of said resin composition is improved and theresulting molding material can be stored for a long time while moldingtime is shortened since water content of said resin compositiondecreases, and puncture phenomenon by vapor is avoided when said moldingmaterial is molded by hot pressing. Further, after said molding materialis molded by hot-pressing, since said resin composition is completelycured, a molded article having an excellent dimension stability and heatresistance is obtained.

[0072] [Molding/Molding Article]

[0073] Since phenolic resin and epoxy resin which are thermosettingresins respectively, are impregnated in said molding material (1) of thepresent invention, said molding material (1) has moldability and isusually molded by hot-pressing using a molding machine having a lowermold part and an upper mold part whose mold faces have desirable shapesrespectively. About the condition of said hot-pressing, presstemperature and press time are respectively settled so that said resincomposition is completely cured and press pressure is usually settled inthe range between 1 and 10 kg/cm². In this case, a sheet can be put onsaid molding material when said molding material is hot-pressed to be alaminated molding article.

[0074] Since said resin composition impregnated in said molding materialdoes not use formaldehyde and formaldehyde donor such ashexamethylenetetramine as a curing agent, formaldehyde is not emittedwhen or after said resin composition is cured so that said moldingmaterial does not contaminate environment.

[0075] Said molded article made from said molding material (1) is usefulespecially as interior of a car such as door trim, a dash board, headlining, insulator hood, dash inner, dash outer, engine under cover,trunk side trim and the like or base member or surface member of saidinterior or building material such as floor panel, wall panel, basepanel of roof and the like.

[0076] When said molded article is used as surface member, waddingmember such as foamed plastic, non-woven fabric and the like may belaminated or the back side of said surface member and said base memberon which said surface member is attached is such as plastic foams (e.g.polyurethane foam, polyolefin foams such as polyethylene foam,polypropylene foam, polyvinyl chloride, polystyrene foam, melamine resinfoam, urea resin foam); corrugated cardboard, resin felt, plywood,particleboard, woody cement board and the like.

[0077] In a case where said molded article is used as a surface member,said surface member is attached on said base member by three methodsdescribed below. The first method is one consisting of molding said basemember (11) into an estimated shape and further molding sheet typemolding material (1) into a shape corresponding with that of said basemember (11), then attaching said molded cured sheet (12) to the surfaceof said base member (11).

[0078] To attach said cured sheet (12) to the surface of said basemember (11), adhesive described below, hot-melt type adhesive, or ahot-melt sheet is used and in a case where said base member (11) is madeof thermoplastic material, said cured sheet (12) is attached by meltingthe surface of said base member (11) by heating.

[0079] The second method is one consisting of putting said sheet typemolding material (12 a) on unmolded base member (11 a) and molding saidsheet type molding material (12 a) and said unmolded base member (11 a)together by hot-pressing using the upper mold part (13) and the lowermold part (14) whose mold faces have desirable shapes respectively tocure said resin composition in said molding material (12 a) as shown inFIG. 2. In this case, a hot melt sheet or adhesive such as naturalresin, natural rubber, synthetic resin, synthetic rubber and the likecan be put between said molding material (12 a) and said unmolded basemember (11 a) according to material of said base member. The thirdmethod is one consisting of molding and curing said sheet type moldingmaterial in an estimated shape, setting said molded and cured sheet typemolding material (12) on the mold face (151) of a mold (15), injectingfoamable liquid resin R in said mold (15), and foaming and curing saidfoamable liquid resin R to form a base as shown in FIG. 3.

[0080] Said foamable liquid resin R includes such as polyurethane resin,polyolefin resin such as polyethylene, polypropylene, and the like,foamable polyvinyl chloride resin, foamable polystyrene resin, foamablemelamine resin, foamable urea resin, and the like, further said resincomposition of the present invention.

[0081] Since said resin composition which does not contain formaldehydeand formaldehyde donor such as hexamethylenetetramine and the like isimpregnated and cured in said surface member of the present invention,said molding material does not emit formaldehyde, not to contaminateenvironment.

[0082] Further since said surface member has a high rigidity, theresulting interior has a good dimension stability to keep the moldedshape for a long time.

[0083] In a case where said molded article is used as the base member ofthe interior, usually the surface member is attached on the surface ofsaid base member.

[0084] The surface members include artificial hides, leathers, knitteditems, textiles, nonwoven fabrics, laminate thereof. The laminate may belaminated with plastics foams such as polyurethane foam, polyethylenefoam, polypropylene foam, polystyrene foam, polyvinylchloride foam andthe like.

[0085] The surface member is pasted on the base member by adhesives, hotmelt adhesives, hot melt sheets and the like.

[0086] The adhesives include acrylic adhesives, synthetic adhesives,elastomer adhesives, vinyl acetate adhesives, vinyl chloride adhesives,urea resin adhesives, melamine resin adhesives, epoxy resin adhesives,and adhesives for use in this resin composition. In this invention, theresin composition can use for an adhesive.

[0087] In the case of forming products, the surface member containing acondensation pre-polymer of thermosetting resins being B-stage may belaminated with the base member so that the surface member can adhere tothe base member.

[0088] Also the adhesives may coat the surface member impregnated withthe thermosetting resin in order to use the adhesives and thethermosetting resin at the same time.

[0089] The hot melt adhesives include polyolefin resins such aspolyethylene, polypropylene, ethylene/vinyl acetate copolymer,ethylene/ethylacrylate copolymer, modified polyolefin resins,polyurethane resin, polyester resin, polyamide resin, mixtures thereof.

[0090] The hot melt adhesives may be prepared as a solution, an emalsionor a dispersion made of the hot melt adhesive powder dispersed in water.Further the hot melt adhesives may use for a sticker.

[0091] In a case where said adhesive is coated to form an adhesivelayer, according to circumstances, said adhesive layer is desirablydotted on the attaching face of said base member. As above described, ina case where said surface member and said base member are attachedtogether by said dotted adhesive layer, the rigidity of said adhesivelayer does not effect the molded shape of the resulting interior and theembossing shape of the surface of the resulting interior, andaccordingly the molded shape of said interior and the embossing shape ofthe surface of said interior are sharply formed. Further, in a casewhere said surface member has gas permeability, since said dottedadhesive layer also has gas permeability, an interior having anexcellent soundproof property is obtained.

[0092] To form said dotted adhesive layer on the adhesive face of saidsurface member, and/or said base member, for instance, a spray coatingmethod, relief printing method, silk screen printing method and the likeare applied and further a method consisting of covering a masking sheeton the adhesive surface; coating the adhesive with such as a spray,knife coater, roll coater, flow coater and the like, and peeling saidmasking member from said adhesive surface also can be applied.

[0093] A desirable method to form said dotted adhesive layer on saidadhesive surface is a spray coating method using a dispersion of a hotmelt adhesive powder

[0094] Said surface member is attached on the surface of said basemember by said adhesive layer and in the case of solution or emulsiontype adhesive, said surface member and said base member are attachedtogether before said adhesive layer is completely dried. Further, in thecase of hot-melt adhesive, said adhesive layer on the adhesive face isheated to soften said adhesive layer and then said surface member andsaid base member are attached together.

[0095] Molding of said base member may be carried out when or after saidsurface member is attached on said base member.

[0096] In a case where said surface member has gas permeability andmolding is carried out after said surface member is attached on saidbase member, since the air contained in said base member is smoothlydischarged from said surface member through said dotted adhesive layerduring molding no puncture phenomenon of the resulting interior occurs.Since said base member of the interior made of said molding material (1)of the present invention contains said resin composition in whichformaldehyde or formaldehyde donor such as hexamethylenetetramine andthe like as a curing agent is not impregnated, the resulting interiordoes not emit formaldehyde not to contaminate the environment. Theresulting interior using said molding material (1) as said base materialhas a high rigidity and has various kinds of use such as the interior ofthe trunk room and the dash board, and the like of a car. In saidinterior, especially in a case where said surface member and said basemember are attached together by said dotted adhesive layer, the rigidityof said adhesive layer does not effect molding shape of said interior orembossing shape of the surface of said interior so that said moldingshape of said interior and embossing shape of the surface of saidinterior become sharp. Further in a case where said surface member hasgas permeability, since said dotted adhesive layer also has gaspermeability, the resulting interior has an excellent soundproofproperty.

[0097] [Chip/Powder/Fiber]

[0098] The chip used as said molding material (2) of the presentinvention includes mainly such as wood flake, saw dust, wood fiberbundle and the like and besides said wood materials, plastic chip,foamed plastic chip and the like can be used as said chip of the presentinvention. The powder used as said molding material (2) of the presentinvention includes wood powder, plastic powder, and the like.

[0099] The fiber used as said molding material (2) of the presentinvention includes natural fiber, organic fiber, inorganic fiber,reclaimed fiber and wood fiber such as wood pulp. Two or more kinds ofsaid chip, powder, fiber may be mixed together to use as said moldingmaterial (2) of the present invention.

[0100] [Preparation of Said Molding Material (2)]

[0101] Said molding material (2) of the present invention is prepared bya method wherein said chip and/or powder and/or fiber is(are) dipped insaid resin composition of the present invention or a method wherein saidresin composition is added with a spray and the like in said chip and/orpowder and/or fiber by stirring and if desired, the resulting mixture isdried by heating at a temperature below the curing temperature of saidresin composition. In this case, said phenolic resin in said resincomposition may be in B-stage the same as said molding material (1).

[0102] [Molding/Molded Article]

[0103] After drying or without drying, said molding material (2) of thepresent invention is strewed on the lower mold having a desirable shapedmold face of the press machine to form a mat and then said mat ishot-pressed. Conditions of said hot-press are the same as the conditionsin the case of said molding material (1) and a sheet may be put on saidmat to hot-press to manufacture a laminated molding article.

[0104] Since said molding material (2) contains said resin compositionwhich dose not use formaldehyde or formaldehyde donor such ashexamethylenetetramine and the like as a curing agent, said moldingmaterial (2) also does not emit formaldehyde when or after said moldingmaterial is cured, not to contaminate the environment.

[0105] The molded article made of said molding material (2) of thepresent invention is useful as the interior as the base member of theinterior the same as said molding material (1) or building material suchas a floor panel, wall panel, base panel of a roof and the like. Saidresin composition is also useful as adhesive, vehicle of paint besidessaid molding material. Further said molding material is used as padmember of the sheet or the mat and the like besides the interior or thebuilding materials.

[0106] [Action]

[0107] When epoxy compound is mixed in phenolic resin, OH group of saidphenolic resin and epoxy group of said epoxy resin react together toform a three dimensional structure below described and as the result,said resin composition is cured.

[0108] Phenolic OH has a tendency to dissociate as follows

[0109] So that said curing reaction can be carried out at a lowtemperature and especially in the case of novalak type phenolic resinsaid reaction can be smoothly and swiftly carried out. In said curingreaction, formaldehyde or formaldehyde donor is not used as a curingagent, the content of free phenol in said phenolic resin also decreases.Further, since the phenol contained in phenolic resin reacts with theepoxy group in epoxy compound in the same manner as described above, thecontent of free phenol in said resin also decreases.

EXAMPLE 1

[0110] An aqueous dispersion of bisphenol A type epoxy resin (50% byweight) (B) using a surface active agent as a dispersing agent was addedin 100 parts by weight (hereafter to be described as “Part(s)”) of 50%by weight of aqueous solution of sulfomethylatedalkylresorcine—formaldehyde precondensate (A) to prepare samples 1 to 6.Adding weight ratio of said aqueous dispersion (B) for each sample isshown in Table 1. A film was formed by using each sample and said filmwas cured at 180° C. for 2 minutes and free formaldehyde was detectedand the result is shown is in Table 1.

Comparison 1

[0111] Novolak type phenolic resin powder (a) in which 5% by weight ofhexamethylenetetramine was mixed was cured in the same manner as inEXAMPLE at 180° C. for 2 minutes and free formaldehyde was detected andthe result is also shown in Table 1. TABLE 1 1 2 3 4 5 6 the ratio ofmixtures (A) 100 100 100 100 100 — (parts by weight) (B) 2 10 50 80 100— (a) — — — — — 100 free formaldehyde 0.15 <0.002 <0.002 <0.002 <0.0025.0 (μg/g)

[0112] Referring to Table 1, it is recognized that free formaldehydecontent of said resin composition of the present invention is muchsmaller than that of the the traditional phenolic resin.

EXAMPLE 2

[0113] PH of 50% by weight of aqueous solution of sulfimethylatedorcinol-phenol formaldehyde precordensate was adjusted by hydrochloricacid and sodium hydroxide as shown in Table 2.

[0114] An aqueous solution of glycidylether type water soluble epoxyresin (50% by weight)(C) and bisphenol F type water soluble epoxy resin(98% by weight) (D) were mixed in said aqueous solution whose pH wasadjusted as above described without using the surface active agentwherein 50 parts of said epoxy resin (C) as solid and 50 parts of saidepoxy resign (D) as solid were added in 100 parts of each precondensatesample as solid and compatibilities of the resulting mixtures weredetermined and the results are sown in Table2. TABLE 2 solubility pH(resin) C D 10.2  ⊚ ∘ 8.3 ⊚ ∘ 7.1 ⊚ ∘ 5.4 ⊚ ∘ 3.2 ⊚ ∘ 1.3 ⊚ ∘

Comparison 2

[0115] Unsulfomethylated orcinol-phenol-formaldehyde pre-co-condensatewas used and mixed in the same manner as in EXAMPLE 2 and the result wasshown in Table 3. Referring to Table 3, in the case of unsulfomethylatedorcinol-phenol-formaldehyde pre-co-condensate, water insoluble epoxyresin can not be stably dispersed in water without using the surfaceactive agent and even in a case where water soluble epoxy resin is used,the resulting dispersion becomes unstable especially in a case where PHvalue is low. TABLE 3 solubility pH (resin) C D 10.2  Δ x 8.3 Δ x 7.1 Δx 5.4 Δ x 3.2 x x x 1.3 x x x

EXAMPLE 3

[0116] Free formaldehyde of the film of the mixture of the water solubleepoxy resin (c) in EXAMPLE 2, said film being cured at 200° C. for 60seconds was detected and the result was shown in Table 4. As shown inTable 4, small amount of free formaldehyde was detected. TABLE 4 freeformaldehyde pH (resin) (μg/g) 10.2 <0.005 8.3 <0.002 7.1 <0.002 5.4<0.002 3.2 <0.002 1.3 0.003

EXAMPLE 4

[0117] Forty-five parts of 60% by weight of aqueous solution ofglycidylamine type water soluble epoxy resin, 5 parts of flameretardant, and 7 parts of oil repellant agent were added to 100 parts of60% by weight of aqueous solution of sulfimethylatedalkylresorcine-phenol-formaldehyde co-condensate with stirring toprepare a uniform solution and said solution was impregnated in a porousmaterial (300 g/m² unit weight) which is non woven fabric of fibermixture (polyester fiber/acrylic fiber =80/20 weight ratio) in an amountof 20 g/m² as solid content. Said porous material in which said solutionwas impregnated was heated at 60 ° C. for 10 minutes to put said resincomposition in B-stage at then press-molded by heating at 190° C. for 3minutes to obtain a molded article having a good strength.

EXAMPLE 5

[0118] Thirty parts of 50% by weight of aqueous solution of diglycidylresorcinol type water soluble epoxy resin and 10 parts of wheat flourwere added in 100 parts of 50% by weight of aqueous solution of novolaktype sulfomethylated alkyl resorcine-formaldehyde pre-condensate toprepare an adhesive. Using said adhesive, a plywood was prepared underthe conditions below described.

[0119] The properties of the resulting plywood were determined and theresults were shown in Table 5. Material: Lauan 2.5 × 2.5 × 2.5 3 plyCoating amount: 35 g/30 × 30 cm Cooling time: 15 minutes Hot press: 120°C., 4 minutes, 10 kg/m²

[0120] TABLE 5 adhesive strength Normal adhesion (Kg/cm²) 20.3 (100)After continuous boiling for 72 hrs 15.1 (100) free formaldehyde (μg/g)<0.002

[0121] Referring to Table 5, a plywood which has an excellentdelamination strength and contains small amount of free formaldehyde wasobtained.

EXAMPLE 6

[0122] Fifteen parts of 40% by weight of glycidylether type aqueoussolution of glycidylether type water soluble epoxy resin was added to100 parts of 40% by weight of sulfimethylated alkylresorcine-in-cresol-formaldehyde pre-co-condensate to prepare a paint.Said paint was coated or the surface of an iron panel at an amount of100 g/m² and then dried at 50° C. for 30 minutes followed by curing at180° C. for 20 minutes. The resulting coating film on said iron panelhas a high surface hardness, an excellent adhesiveness, an excellentwater resistance, and an excellent weather resistance.

EXAMPLE 7

[0123] Fifty parts of polyethyleneglycol diglycidyl ether and oil partsof stearic acid were added to 100 parts of 60% by weight of aqueoussolution of sulfimethylated alkyl resorcine phenol-formaldehydepre-co-condensate to mix uniformly and the resulting mixture was dilutedby water to be 10% by weight of solid content. The resulting aqueoussolution was impregnated in a paper by pressing with a roller and thendried at 100 to 120° C. for 5 minutes. Ten pieces said papers werelaminated together and molded by hot-pressing of 100 kg/cm² at 200° C.to prepare a laminated panel having an excellent mechanical properties.

EXAMPLE 8

[0124] One hundred parts of said resin composition prepared in EXAMPLE 1was sprayed to 100 parts of mixture of wood flake and wood powder (80:20weight ratio) and mixed by stirring. The resulting mixture was scatteredon the lower mold part of the press-molding machine to form a mat andsaid mat was press-molded between the lower mold part and the upper moldpart at 180° C. for 5 minutes with a pressing pressure 3 kg/cm² toprepare a wood fiber panel. Said wood fiber panel has a high strengthand small amount of free formaldehyde.

EXAMPLE 9

[0125] Formaldehyde sodium sulfoxylate (Rongalit) (0.4 moles) and 1 moleof caustic soda were added to 1 mole of bisphenol A with water andreacted at 50° C. for 2 hours and then at a temperature between 95 and100° C. for 5 hours. After that 1.7 moles of epichlorohydrin and 1.5moles of caustic soda were added and reacted at a temperature between 50and 60° C. for 5 hours followed by separation of water and impurities toprepare sulfimethylated epoxy resin (E).

[0126] Twenty-five parts of 60% by weight of aqueous solution ofphenol-formaldehyde pre-condensate, 5 parts of 40% by weight of paraffinwax emulsion and 400 parts of water were added to 70 parts of saidsulfimethylated epoxy resin (E) to mix uniformly to prepare an aqueousdispersion. Said aqueous dispersion was sprayed to glass fiber (coatingamount: 10% by weight for glass fiber).

[0127] After said spray coating, said glass fiber was dried at atemperature between 80 and 90° C. for 10 minutes to remove water thereinand then molded by hot-press at 180° C. for 5 minutes to prepare amolded article having a high rigidity.

EXAMPLE 10

[0128] Phenol (1 mole), 37% by weight aqueous solution of formaldehyde(1.5 moles), caustic soda (0.1 moles) and sodium sulfite (0.3 moles)were mixed and reacted together at 85° C. for 8 hours to producesulfimethylated phenol-formaldehyde pre-condensate (F), 10 parts ofmelamine was added to 100 parts of said pre-condensate (F) (solidcontent 50% by weight) by stirring to mix uniformly and further 50 partsof sulfimethylated epoxy resin (E) prepared in EXAMPLE 9 was added. Theresulting mixture was impregnated in glass fiber mat (unit weight 300g/m²) in an amount of 200 g/m² and said mat was dried at 80° C. for 20minutes followed by hot pressing at 170° C. for 5 minutes to prepare amolded article having a high rigidity.

EXAMPLE 11

[0129] Phenol (1 mole), 37% by weight aqueous solution of formaldehyde(1.5 moles), caustic soda (0.1 moles), and sodium sulfite (0.3 moles)were mixed and reacted together at 85° C. for 7 hours to producesulfomethylated phenolic resin pre-condensate and then urea (0.5 moles)was added to said pre-condensate to react together for 2 hours toproduce sulfomethylated phenol-urea-formaldehyde pre-co-condensate. Onehundred parts of sulfimethylated epoxy resin (E) prepared in EXAMPLE 9and 300 parts of water were added to 100 parts of said pre-condensate(solid content 45%) by stirring to prepare an uniform solution. Saidsolution was coated to glass fiber mat (unit weight 40 g/m²) by a sprayin an amount of 100 g/m². After coating, said mat was dried at 100° C.for 5 minutes and then a pair of said mats were put on the both sides ofa corrugated board. The resulting laminated board was molded byhot-pressing at 160° C. for 2 minutes to prepare a molded article havinga high rigidity.

Industrial Applicability

[0130] The present invention provides a resin composition emitting lesstoxic material such as free formaldehyde and free phenol when and aftersaid resin composition is molded and said resin composition is cured ata low temperature, and being useful as molding material, binderadhesive, paint and the like.

What is claimed is
 1. (canceled)
 2. (canceled)
 3. (canceled) 4.(canceled)
 5. (canceled)
 6. (canceled)
 7. (canceled)
 8. (canceled) 9.(canceled)
 10. (canceled)
 11. (canceled)
 12. (canceled)
 13. (newlyadded) A molding material comprising a porous material impregnated witha resin composition comprising mixture of aqueous solution of phenolicresin and epoxy compound.
 14. (newly added) A molding material inaccordance with claim 13, wherein said phenolic resin is co-condensatewith aminoplast monomer and/or its precondensate.
 15. (newly added) Amolding material in accordance with claims 13 to 14, wherein saidmixture is mixed with aminoplast and/or its aminoplast monomer. 16.(newly added) A molding material in accordance with claims 13 to 15,wherein said epoxy compound is dispersed or emulsified in water and thenmixed in said aqueous solution of phenoric resin.
 17. (newly added) Amolding material in accordance with claims 13 to 16, wherein saidphenolic resin is partially or wholly sulfoalkylated and/orsulfialkylated.
 18. (newly added) A molding material in accordance withclaims 13 to 17, wherein said epoxy compound is an epoxy resin. 19.(newly added) A molding material in accordance with claim 18, whereinsaid epoxy resin has aryl group and said aryl group is partially orwholly sulfoalkylated and/or sulfialkylated.
 20. (newly added) A moldingmaterial in accordance with claims 13 to 19, wherein said phenolic resinin said resin composition is to be B-stage.
 21. (newly added) A moldedarticle manufactured by molding said molding material in accordance withclaims 13 to 20, with heating in a designated shape to cure said resincomposition in said molding material.
 22. (newly added) A moldingmaterial comprising chip and/or powder and/or fiber material, in which aresin composition comprising mixture of aqueous solution of phenolicresin and epoxy compound is mixed as a binder.
 23. (newly added) Amolding material in accordance with claim 22, wherein said phenolicresin is co-condensate with aminoplast monomer and/or its precondensate.24. (newly added) A molding material in accordance with claims 22 to 23,wherein said mixture is mixed with aminoplast and/or its aminoplastmonomer.
 25. (newly added) A molding material in accordance with claims22 to 24, wherein said epoxy compound is dispersed or emulsified inwater and then mixed in said aqueous solution of phenolic resin. 26.(newly added) A molding material in accordance with claims 22 to 25,wherein said phenolic resin is partially or wholly sulfoalkylated and/orsulfialkylatd.
 27. (newly added) A molding material in accordance withclaims 22 to 26, wherein said epoxy compound is an epoxy resin. 28.(newly added) A molding material in accordance with claim 27, whereinsaid epoxy resin has aryl group and said aryl group is partially orwholly sulfoalkylated and/or sulfialkylated.
 29. (newly added) A moldedarticle manufactured by molding said molding material in accordance withclaims 22 to 28, with heating in a designated shape to cure said resincomposition in said molding material.